On the nature of Cu-carbon interaction through N-modification for enhanced ethanol synthesis from syngas and methanol
Direct conversion of syngas into ethanol is an attractive process because of its short route and high-added value, but remains an enormous challenge due to the low selectivity caused by unclear active sites. Here, the Cu(111) supported N-modified graphene fragments C N /Cu(111) ( = 0-2) are demonstr...
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Veröffentlicht in: | Physical chemistry chemical physics : PCCP 2024-07, Vol.26 (30), p.20470-20482 |
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Sprache: | eng |
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Zusammenfassung: | Direct conversion of syngas into ethanol is an attractive process because of its short route and high-added value, but remains an enormous challenge due to the low selectivity caused by unclear active sites. Here, the Cu(111) supported N-modified graphene fragments C
N
/Cu(111) (
= 0-2) are demonstrated to be an efficient catalyst for fabricating ethanol from syngas and methanol. Our results suggest that the Cu-carbon interaction not only facilitates CO activation, but also significantly affects the adsorption stability of C
intermediates and finally changes the fundamental reaction mechanism. The impeded hydrogenation performance of C
/Cu(111) due to the introduced Cu-carbon interaction is dramatically improved by N-doping. Multiple analyses reveal that the promoted electron transfer and the enhanced electron endowing ability of C
N
/Cu(111) (
= 1-2) to the co-adsorbed CH
CH
OH (
= 0-1) and H are deemed to be mainly responsible for the remarkable enhancement in hydrogenation ability. From the standpoint of the frontier molecular orbital, the decreased HOMO-LUMO gap and the increased overlap extent of HOMO and LUMO with the doping of N atoms also further verify the more facile hydrogenation reactions. Clearly, the Cu-carbon interaction through N-modification is of critical importance in ethanol formation. The final hydrogenation reaction during ethanol formation is deemed to be the rate-controlling step. The insights gained here could shed new light on the nature of Cu-carbon interaction in carbon material modified Cu-based catalysts for ethanol synthesis, which could be extended to design and modify other metal-carbon catalysts. |
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ISSN: | 1463-9076 1463-9084 1463-9084 |
DOI: | 10.1039/d4cp01599a |